Journal of Alloys and Compounds: Soraya Darafarin, Reza Sahraei, Ali Daneshfar
Journal of Alloys and Compounds: Soraya Darafarin, Reza Sahraei, Ali Daneshfar
Journal of Alloys and Compounds: Soraya Darafarin, Reza Sahraei, Ali Daneshfar
a r t i c l e i n f o a b s t r a c t
Article history: ZnS:Ni thin films with high purity in composition and crystallographic sense were deposited by chemical
Received 10 August 2015 bath deposition method at temperatures ranging from 40 to 80 C. The effect of deposition temperature
Received in revised form on the average crystal size, lattice constant, lattice strain, optical, and photoluminescence properties of
27 October 2015
the films is followed and discussed. The band gap energy of the ZnS:Ni thin films deposited at 40 C is
Accepted 29 October 2015
blue-shifted by about 0.14 eV with respect to the bulk value, while with increasing deposition temper-
Available online 9 November 2015
ature to 80 C it converges to 3.6 eV. The photoluminescence (PL) spectra of the ZnS:Ni thin films
exhibited three emission peaks, two intense peaks located at 430 nm and 523 nm and a weak shoulder
Keywords:
Nanostructured materials
peak over 325e400 nm range. The intensity of photoluminescence emission is enhanced with increasing
Semiconductors deposition temperature. X-ray diffraction analysis shows that the ZnS:Ni films constituted from nano-
Thin films crystals possessing average radii close to, and partially larger than, the radius of a bound exciton in the
Optical properties corresponding bulk semiconductor. Finally, a subsequent analysis based on effective mass approximation
model permits determination of the reduced effective mass of the electronehole pair ðm*eff Þ and the
relative dielectric constant (εr) for the ZnS:Ni nanocrystals in thin film from.
© 2015 Elsevier B.V. All rights reserved.
1. Introduction new electronic states and can assist in the creation of new optical
centers to produce different colored emissions [14]. In the other
Zero-dimensional nanoscale materials such as quantum dots words, the Ni2þ ions induce new impurity states at different posi-
and semiconductor nanocrystals exhibit interesting and useful tions within the host band gap and strongly interfere with the
properties and may be applied in thin films form for the fabrication existing carrier recombination process [12]. As a consequence, the
of the next generation of nanoelectronic and nanooptic devices [1]. recombination process occurs via these newly induced electronic
Among the various nanocrystalline semiconductors, zinc sulfide states and results in different emission colors [18].
(ZnS) has attracted intensive studies due to its potential applica- The chemical bath deposition (CBD) method has been used for
tions in many optoelectronic and photovoltaic technologies such as the doping of various transition metals ions into the ZnS host
light emitting diodes, sensors, and thin film solar cells [2e6]. crystals in thin film form [19e27]. However, there are few reports
Pure ZnS crystals have large band gap energy of about 3.6 eV for the specific deposition of Ni doped ZnS thin films by the CBD
(cubic zinc blende phase) and therefore their applications are method [16,28e30]. Huang et al. [28] reported the preparation of
limited to blue and ultraviolet light emitting devices [7,8]. When the undoped and Ni doped ZnS thin films on ITO-coated glass
transition metals (dn) ions are doped into the ZnS host crystals, the substrates at 80 C using the sodium citrate as complexing agent in
optical, electrical, and magnetic properties of the host lattice are alkaline bath (pH > 11). They reported that doping of the ZnS thin
improved [9e13]. Recently, nickel doped zinc sulfide (ZnS:Ni) films with Ni leads to a considerable red shift in absorption edge of
nanocrystals have attracted more attention because of their tunable the UVevis spectra. The band gap values obtained by Huang et al.
fluorescence emission and low temperature ferromagnetic prop- for the undoped and Ni doped ZnS films were in the range of
erties [13e17]. It is known that, the Ni2þ ions as dopant can create 3.37e3.02 eV which were somewhat smaller than the typical value
of bulk ZnS (~3.6 eV). They have concluded that the decrease of the
band gap is probably related to the annealing effect and the
deformation of the films structure. In addition, they have investi-
* Corresponding author. gated and compared the photoelectrical properties of the undoped
E-mail addresses: r.sahraei@ilam.ac.ir, reza_sahrai@yahoo.com (R. Sahraei).
http://dx.doi.org/10.1016/j.jallcom.2015.10.272
0925-8388/© 2015 Elsevier B.V. All rights reserved.
S. Darafarin et al. / Journal of Alloys and Compounds 658 (2016) 780e787 781
and Ni doped ZnS thin films in details. Recently, Akhtar and co- excitation of the ZnS:Ni films in the UV region. All measurements
workers [29] have prepared the Ni doped ZnS thin films by CBD were carried out at room temperature.
method at 80 C and in acidic solution (pH ¼ 3.8). They have
studied the ferromagnetic and half metallic properties of the 3. Results and discussion
deposited films based on experimental results and theoretical cal-
culations in details. In our previous works, we have deposited the 3.1. Elemental analysis
ZnS:Ni thin films in a weak acidic bath (pH ¼ 6.0) at 80 C and the
effect of Ni doping on compositional, morphological, structural, and Chemical composition of ZnS:Ni thin films were analyzed by
optical properties of the films has been investigated in details EDX and ICP-AES measurements. EDX analysis identified the pres-
[16,30]. Nevertheless, to the best of our knowledge, no evidence of ence of zinc, sulphur, and silicon for all the layers deposited (Fig. 1).
the effect of deposition temperature on the structural and optical The signal of silicon comes from the silicon substrate. The Zn/S
properties of the Ni doped ZnS thin films prepared by the CBD atomic ratios for the prepared thin films were summarized in
method have been reported. Table 1. As can be seen, the variation of the Zn/S atomic ratios for all
In the present study, the Ni doped ZnS thin films were deposited thin films deposited at different temperatures is small and the Zn/S
by the CBD method at temperatures ranging from 40 to 80 C at pH atomic ratios are almost close to their stoichiometry. As the actual
of 6. The weak acidic bath (pH of 6.0) is chosen to avoid the for- concentration of Ni doped in all of the films was less than the
mation of undesired species such as ZnO and/or Zn(OH)2 in the detection limit of EDX, therefore, the Ni concentration in the ZnS:Ni
films [16,20,31,32]. The aim of this present work is to study the films was determined by ICP-AES measurements. The obtained Ni/
effect of deposition temperature on the structural, optical and Zn atomic percent ratios for the ZnS:Ni films deposited at 40, 60
photoluminescence properties of the ZnS:Ni thin films. The films and 80 C for 8 h were also listed in Table 1. ICP-AES analysis shows,
are characterized by several techniques such as X-ray diffraction, with increasing in deposition temperature, the Ni/Zn atomic ratios
field emission scanning electron microscopy (FE-SEM), optical in the films increase. It should be noted that a very weak peak (less
transmittance and fluorescence spectrophotometer. Measure- than the detection limit of EDX) at around 1 KeV in the EDX spec-
ments, such as those outlined above, allow quantitative analysis of trum (Fig. 1) could be corresponding to trace amounts of oxygen in
the increase in band gap energy due to quantum confinement ef- the films. According to our previous works, this very small amount
fects between the conduction and valence bands. A subsequent of oxygen is related to adsorbed water on the films as it has been
analysis of these data permits determination of the reduced detected by FT-IR and XPS analysis [16,20,31,32]. The co-deposition
effective mass of the electronehole pair and the relative dielectric of ZnS and NiS quite difficult, because of the ZnS (Ksp ¼ 1.1 1024)
constant for the ZnS:Ni nanocryatals in thin films from. These is much less soluble than the NiS (Ksp ¼ 1.1 1020). During the
values are compared, where available, with previously determined deposition process, ZnS can forms the main phase, whereas Ni2þ
values for the bulk ZnS. ions are present as an impurity and can be incorporated gradually
into the ZnS crystal lattice, depending on the deposition
2. Experimental temperature.
Table 1
The film thickness, t, Zn/S and Ni/Zn ratios, the lattice constant, a, the lattice strain, h, the average crystal size, D, and the band gap energy, Eg, values for the ZnS:Ni films
deposited at the different temperatures.
Temp.( C) t (nm) Zn/S (at ratio) Ni/Zn (at %) a (nm) h D (nm) Eg (eV)
. 1=2
dhkl ¼ a h2 þ k2 þ l2 and nl ¼ 2dhkl sin qhkl (1)
On the basis of data for all peaks in the X-ray diffractograms of the
ZnS:Ni thin films prepared at different deposition temperatures,
the corresponding values of the lattice constant (a) were calculated.
Fig. 2. XRD patterns of the ZnS:Ni films deposited at different deposition Then, in order to avoid from random and systematic errors on
temperatures. the measurement of qhkl, the result is plotted against
FðqÞ ¼ cos2 q=sin q þ cos2 q=q (Fig. 4). By vertical intercept of the
straight-line fit of diagrams in the Fig. 4, the precise values of the
correspond to (111), (220), and (311) planes; the peaks position lattice constant (a) for the ZnS:Ni thin films deposited at different
match well with the standard pattern of the ZnS cubic phase [32]. temperatures are obtained [32,36]. The results are given in Table 1.
The diffraction peaks in all diffractograms are relatively broadening As can be seen, the lattice constants for the ZnS:Ni thin films
due to finite crystalline size of the ZnS:Ni thin films [33]. It is worth deposited at different temperatures are slightly smaller than that
noting that, no diffraction peaks correspond to NiS has been reported for the bulk ZnS cubic structure (0.5406 nm), and it con-
detected, indicates that the Ni2þ ions preferably incorporated into verges to the bulk value upon increasing deposition temperature.
the ZnS lattice and there is no secondary phase in the structure of As can be seen in Fig 2, the X-ray diffraction patterns for all thin
thin films. Also, no characteristic peaks related to the impurity films deposited at different deposition temperature are relatively
phases such as ZnO and/or Zn(OH)2 were detected in the ZnS:Ni broad. Tow important factor play basic role on the broadening of X-
thin films. It is clearly visible from Fig. 2, for the deposited film at ray diffraction peaks. One of these factors is the approximate crystal
80 C, the intensity of diffraction peaks are relatively stronger than diameter (D) and another is the lattice strain (h). In order to eval-
that of the films deposited at low temperatures. This suggests that uate the contribution of each of these two factors, we start by
the following factors are contributed in such behavior for the thin expressing the overall broadening (b) of the XRD peaks by the
films [34]: following relation [37,38]:
i the deposited films at high temperature have more thickness. In b cos q ¼ 4h sin q þ Kl=D (3)
fact, the films with high thickness show the diffraction peaks
with high intensity in the XRD patterns. where, K is the shape factor in spherical approximation which is
ii at high deposition temperature, the bigger nanocrystals is approximately unity, l is the wavelength of the used X-ray radia-
grown. This temperature dependence of nanocrystals size may tion, q is the angle correspond to the diffraction maximum, and b is
be explained on thermodynamic grounds of larger crystallites the full-width at half-maximum (FWHM) of the XRD peaks
being more stable than the smaller ones which are more favored appearing at the diffraction angle q. The b parameter in the above
kinetically at lower temperatures. equation must be corrected with the instrumental width through
iii at high deposition temperature, the Ni2þ ions are more incor- using of the geometric mean [39]:
porated into the vacancy states of the host matrix, therefore, the
degree of crystallinity of the ZnS:Ni thin films is improved. 1=2
1=2
b¼ bexp binst b2exp b2inst (4)
The cross-sectional view of SEM images for the ZnS:Ni thin films
deposited on glass substrate at deposition temperatures of 40 and
where, bexp and binst parameters are the experimental and the
80 C was shown in Fig. 3(a and b), respectively. It can be also seen
instrumental linear widths in radians, respectively. The value of
that the thickness of the ZnS:Ni thin films is increased with
binst was determined to be 2.58 103 rad by using a standard
increasing deposition temperature.
silicon powder. Thus, it is clear that when bcosq is plotted against
S. Darafarin et al. / Journal of Alloys and Compounds 658 (2016) 780e787 783
Fig. 3. Cross-sectional SEM images of the ZnS:Ni thin films deposited at 40 C (a) and at 80 C (b).
Fig. 6. SEM images of the ZnS:Ni thin films deposited at 40 C (a) and at 80 C (b).
Fig. 7. (a) PL spectra of the uncoated quartz and the ZnS:Ni film deposited on quartz substrate at 60 C for 8 h, and (b) PL spectra of the ZnS:Ni films deposited at various
temperatures.
bands, two intense bands located at 430 nm and 523 nm and a While the PL emission intensity for the ZnS:Ni films deposited at 60
weak shoulder peak over 325e400 nm range. It is well known that and 80 C was enhanced. The high PL intensity could be related to
the blue emission at 430 nm is related to the defect levels within more incorporation of the Niþ2 ions into the ZnS host crystals as
the band gap, where interstitial sulfur and vacancy states were well as improvement in crystallinity and thickness of the ZnS:Ni
formed during the deposition of nanocrystalline ZnS films. The films deposited at higher temperature [47]. Hence, the more new
similar results were also reported for the blue emission of ZnS radiative centers were generated in the ZnS host crystals at high
nanopraticles in the literature [44,45]. The green emission at deposition temperature. Thus, the decrease of defects density and
523 nm of the ZnS:Ni films can be attributed to the ded optical the increase of radiation centers in the ZnS:Ni films deposited at
transitions of Ni2þ luminescent centers formed in the ZnS host higher temperature play an important role in the improvement of
crystals. When Ni2þ ions incorporate into the ZnS lattice, the lowest their optical and photoluminescence properties. Therefore, the
multiplet term 3F of the free Ni2þ ions is split into 3T1, 3T2, and 3A2 nanocrystalline ZnS:Ni thin films with intense green emission may
through the anisotropic hybridization [11,46]. In summary, the have the potential applications in electroluminescent devices such
photoluminescence in this region is attributed to the 3T2 / 3A2 as large-area displays.
transitions within the 3d shell of Ni2þ ions that incorporated into The optical transmission and reflection spectra of bare glass and
the ZnS lattice. In addition, the weak shoulder UV emission peak in the ZnS:Ni thin films deposited on glass substrates at 40, 60, and
the range of 325e400 nm corresponding to near-band-edge 80 C for 8 h were studied in wavelengths region from 300 to
emission is originated from the recombination of free excitons of 800 nm and shown in Fig. 8 (a). As can be seen, all thin films have
ZnS [18]. high transparency in the visible region. The optical transmittance of
Fig. 7(b) shows the PL emission spectra of the ZnS:Ni films the ZnS:Ni thin films was varied between 45 and 90% in the visible
prepared at different deposition temperatures for 8 h. It well region and was depended on the deposition temperature. The
known that the PL intensity of semiconductors was closely related decrease in the optical transmission of thin films with increasing
to two important factors: the quality of crystals and the abundance temperature can due to enhancement in the films thickness as can
of radiative centers in the films. As shown in Fig. 7(b), the ZnS:Ni be seen from the cross sectional FE-SEM images (Fig. 3(b)).
film deposited at 40 C has the lowest PL intensity. The low in- The absorption edge of the ZnS:Ni thin films is observed at about
tensity of the PL emission was suggested that the crystallinity of the 330e340 nm. The sharp absorption edge is due to the uniform and
ZnS:Ni films was low (as seen in the XRD Pattern), and also the Ni2þ compact morphology of the ZnS:Ni thin films [18]. It can be seen
ions were not incorporated effectively into the ZnS host crystals. In that the absorption edge of the spectra clearly shifted towards
addition, the low thickness (170 nm) of the ZnS:Ni films deposited shorter wavelengths in the lower deposition temperature. This
at 40 C could be another reason for their low PL emission intensity. blue-shift in absorption edge is associated with increasing in the
S. Darafarin et al. / Journal of Alloys and Compounds 658 (2016) 780e787 785
Fig. 8. Optical transmittance and reflectance spectra (a), and dependence of absorption coefficients on incident photon energy (b) of the ZnS:Ni thin films deposited at various
temperatures.
band gap energy of the ZnS:Ni films. Based on the obtained optical
absorbance data, the values of absorption coefficient, a, could be
determined by using the following equation [48,49]:
[5] J. Kim, C. Park, S.M. Pawar, A.I. Inamdar, Y. Jo, J. Han, J.P. Hong, Y.S. Park, [32] R. Sahraei, G. Motedayen Aval, A. Goudarzi, J. Alloys Compd. 466 (2008)
D.Y. Kim, W. Jung, H. Kim, H. Im, Thin Solid Films 566 (2014) 88e92. 488e492.
[6] M. Nguyen, K. Ernits, K.F. Tai, C.F. Ng, S.S. Pramana, W.A. Sasangka, [33] H. Hennayaka, H.S. Lee, Thin Solid Films 548 (2013) 86e90.
S.K. Batabyal, T. Holopainen, D. Meissner, A. Neisser, L.H. Wong, Sol. Energy [34] R. Sahraei, G. Motedayen Aval, A. Baghizadeh, M. Lamehi-Rachti, A. Goudarzi,
111 (2015) 344e349. M.H. Majles Ara, Mater. Lett. 62 (2008) 4345e4347.
[7] J. Chen, F. Xin, S. Qin, X. Yin, Chem. Eng. J. 230 (2013) 506e512. [35] M.T. Weller, Inorganic Materials Chemistry, Oxford University Press, Oxford,
[8] A. Inamdar, S. Lee, D. Kim, K.V. Gurav, J.H. Kim, H. Im, W. Jung, H. Kim, Thin 1997.
Solid Films 537 (2013) 36e41. [36] A.E. Rakhshani, A.S. Al-Azab, Appl. Phys. A 37 (2001) 631e636.
[9] D.E. Ortíz-Ramos, L.A. Gonza lez, R. Ramirez-Bon, Mater. Lett. 124 (2014) [37] E. Lifshin, X-ray Characterization of Materials, Wiley-VCH, New York, 1999.
267e270. [38] B. Pejova, I. Bineva, J. Phys. Chem. C 117 (2013) 7303e7314.
[10] B. Poornaprakash, D.A. Reddy, G. Murali, N.M. Rao, R.P. Vijayalakshmi, [39] C. Suryanarayana, M.G. Norton, X-Ray Diffraction, Plenum Press, New York,
B.K. Reddy, J. Alloys Compd. 577 (2013) 79e85. 1998.
[11] M. Molaei, J. Lumin. 136 (2013) 38e41. [40] B. Pejova, I. Bineva, J. Mater. Sci. Mater. Electron. 26 (2015) 4944e4955.
[12] S. Jana, G. Manna, B.B. Srivastava, N. Pradhan, Small 9 (2013) 3753e3758. [41] B. Pejova, B. Abay, J. Phys. Chem. C 115 (2011) 23241e23255.
[13] J. Kaur, M. Sharma, O.P. Pandey, Opt. Mater. 47 (2015) 7e17. [42] Q. Pan, D. Yang, Y. Zhao, Z. Ma, G. Dong, J. Qiu, J. Alloys Compd. 579 (2013)
[14] D.A. Reddy, D.H. Kim, S.J. Rhee, C.U. Jung, B.W. Lee, C. Liu, J. Alloys Compd. 588 300e304.
(2014) 596e604. [43] V. Ramasamy, K. Praba, G. Murugadoss, Superlattices Microstruct. 51 (2012)
[15] S. Kumar, N.K. Verma, J. Mater. Sci. Mater. Electron. 25 (2014) 1132e1137. 699e714.
[16] R. Sahraei, S. Darafarin, J. Lumin. 149 (2014) 170e175. [44] D. Denzler, M. Olschewski, K. Sattler, J. Appl. Phys. 84 (1998) 2841e2845.
[17] S. Kumar, C.L. Chen, C.L. Dong, Y.K. Ho, J.F. Lee, T.S. Chan, R. Thangavel, [45] S. Wageh, Z.S. Linga, X. Xu-Rong, J. Cryst. Growth 255 (2003) 332e337.
T.K. Chen, B.H. Mok, S.M. Rao, M.K. Wu, J. Alloys Compd. 554 (2013) 357e362. [46] P. Yang, M. Lu, D. Xu, D. Yuan, J. Chang, G. Zhou, M. Pan, Appl. Phys. A 74
[18] S. Jana, B.B. Srivastava, S. Jana, R. Bose, N. Pradhan, J. Phys. Chem. Lett. 3 (2012) (2002) 257e259.
2535e2540. [47] N. Eryong, L. Donglai, Z. Yunsen, B. Xue, Y. Liang, J. Yong, J. Zhifeng,
[19] M.S. Akhtar, Y.G. Alghamdi, M.A. Malik, R.M.A. Khalild, S. Riaz, S. Naseem, S. Xiaosong, Appl. Surf. Sci. 257 (2011) 8762e8766.
J. Mater. Chem. C 3 (2015) 6755e6763. [48] J.I. pankove, Optical Processes in Semiconductors, Dover Pub., New York,
[20] A. Goudarzi, G. Motedayen Aval, S.S. Park, M.C. Choi, R. Sahraei, M. Habib 1967.
Ullah, A. Avane, C.S. Ha, Chem. Mater. 21 (2009) 2375e2385. [49] P. Roy, J.R. Ota, S.K. Srivastava, Thin Solid Films 515 (2006) 1912e1917.
[21] D.E. Ortíz-Ramos, L.A. Gonz alez, R. Ramirez-Bon, Mater. Lett. 124 (2014) [50] M.G. Bawendi, M.L. Steigerwald, L.E. Brus, Annu. Rev. Phys. Chem. 41 (1990)
267e270. 477e496.
[22] A.I. Inamdar, S. Lee, D. Kim, K.V. Gurav, J.H. Kim, H. Im, W. Jung, H. Kim, Thin [51] Y. Wang, N. Herron, J. Phys. Chem. 95 (1991) 525e532.
Solid Films 537 (2013) 36e41. [52] A. Mark Fox, Optical Properties of Solids, Oxford University Press, Oxford,
[23] A.C. Dhanya, K. Deepa, T.L. Remadevi, J. Mater. Sci. Mater. Electron. 24 (2013) 2001.
4782e4789. [53] B. Enright, D. Fitzmaurice, J. Phys. Chem. 100 (1996) 1027e1035.
[24] S. Muthukumaran, M.A. Kumar, Mater. Lett. 93 (2013) 223e225. [54] N. Chestnoy, R. Hull, L.E. Brus, J. Chem. Phys. 85 (1986) 2237e2242.
[25] H.J. Zhu, Y. Liang, X.Y. Gao, R.F. Guo, Q.M. Ji, Braz. J. Phys. 45 (2015) 308e313. [55] P.Y. Yu, M. Cardona, Fundamentals of Semiconductors: Physics and Materials
[26] Y. Chen, G.F. Huang, W.Q. Huang, B.S. Zou, A.L. Pan, Appl. Phys. A 108 (2012) Properties, fourth ed., Springer, Berlin, 2010.
895e900. [56] L. Brus, J. Phys. Chem. 90 (1986) 2555e2560.
[27] M.S. Akhtar, M.A. Malik, Y.G. Alghamdi, K.S. Ahmad, S. Riaz, S. Naseem, Mater. [57] B. Pejova, I. Grozdanov, Mater. Chem. Phys. 90 (2005) 35e46.
Sci. Semicond. process. 39 (2015) 283e291. [58] A.D. Yoffe, Adv. Phys. 42 (1993) 173e266.
[28] C.M. Huang, L.C. Chen, G.T. Pan, T.C.K. Yang, W.S. Chang, K.W. Cheng, Mater. [59] D.R. Vij, N. Singh, Luminescence and Related Properties of II-VI Semi-
Chem. Phys. 117 (2009) 156e162. conductors, Nova Science Pub. Inc, Commack, New York, 1998.
[29] M.S. Akhtar, M.A. Malik, S. Riaz, S. Naseem, Mater. Chem. Phys. 160 (2015) [60] D.R. Vij, Handbook of Electroluminescent Materials, IOP Publishing Ltd, Bris-
440e446. tol, 2004.
[30] R. Sahraei, S. Darafarin, Spectrochim. Acta Part A 149 (2015) 941e948. [61] Y. Wang, A. Suna, W. Mahler, R. Kasowski, J. Chem. Phys. 87 (1987)
[31] R. Sahraei, A. Daneshfar, A. Goudarzi, S. Abbasi, M.H. Majles Ara, F. Rahimi, 7315e7322.
J. Mater. Sci. Mater. Electron 24 (2013) 260e266.